90 Years with PCI: A Retrospective In the 1910s

Chances are the French-born chemist A.J. Rossi had no clue in the early 1900s that his efforts to develop titanium-based alloys for steel would lead to a discovery that would revolutionize coatings technology.

Rossi, according to historical accounts, came to America around 1870 and became involved in the business of smelting titaniferous ores - iron ores containing titanium - into pig iron at a blast-furnace operation located in Boonton, NJ. Rossi gained a reputation as an authority on such smelting processes, and joined a business venture that around 1890 built a blast furnace at Buffalo, NY, where titaniferous ores were smelted. Rossi secured patents on these smelting processes and the manufacture of various titanium alloys.

A few years later, in 1906, Rossi also figured in the launch of a business, the Titanium Alloy Manufacturing Co., that built a plant at Niagara Falls, NY, for the production of ferro carbon titanate, an alloy developed by Rossi for use in steelmaking. In further work involving titanium, Rossi was able to separate an impure titanium oxide. He found that the material produced opacifying properties when mixed in an oil, thus setting in motion a sequence of developments that would lead to the genesis of a multibillion-dollar industry and a cornerstone of modern paint technology.

DuPont Co.’s Edgemoor TiO2 plant site in Delaware, where the company introduced the chloride production process in 1948. The plant is located on land once owned by William Penn, and the site also was formerly occupied by an iron mill that produced girders for the Brooklyn Bridge.

In further work involving titanium dioxide, Rossi and his associates demonstrated the material's efficacy as a white pigment with unique properties. They developed a method of separating TiO2 from ilmenite and rutile ores, and made further strides in the composition of pigments involving combinations with barium sulfate, blanc fixe, calcium sulfate, lead oxide, and magnesium silicate. Their work resulted in the launch, in 1916, of the Titanium Pigment Co. and the construction of a plant at Niagara Falls to produce titanium pigments. Commercial production of pigments was delayed by World War I, but finally began in 1918.

The immense potential of titanium-based pigments as a key paint ingredient was demonstrated early on, with the 1921 development of a TiO2-barium sulfate composition that found use in the paste-type paints popular among master painters of those days. This composite pigment reportedly delivered more than three times the hiding power of the white lead commonly used in these paints.

The titanium production operations carried on by the Titanium Alloy Manufacturing Co. initially used ores recovered from deposits in a remote area of the Adirondack Mountains in upstate New York, about 60 miles from Ticonderoga. Around 1913, titaniferous sand deposits in northern Florida also provided a supply for the company.

Seeing the great promise of titanium-based pigments, the National Lead Co. in 1920 acquired a significant stake in the Titanium Pigment Co. Inc. The companies remained partners until 1932, when National Lead purchased the business outright. Titanium-based pigment, however, had begun to experience rapid demand growth prior to the acquisition by National Lead, resulting in the construction of a second pigment plant, which started operations in 1923 in St. Louis. A third production plant was built in New Jersey, and began operation in 1935. Later, National Lead acquired a Norwegian-based TiO2 company, Titan A/S.

In entering the fledgling titanium-pigment industry, National Lead "saw the handwriting on the wall," one longtime industry veteran observed, referring to early signals that white lead's days as a paint pigment were numbered.

Continued development of titanium-based pigments led to the introduction of pure pigmentary-quality titanium dioxide in 1925, which delivered greater opacity than the original composite pigments. A major early boost for TiO2 came in the 1920s with its incorporation in nitrocellulose lacquers for automotive finishes. Due to a combination of whiteness, opacity, brightness, and nonreactivity, TiO2 pigments enjoyed strong demand growth in varied applications besides paint. These uses include paper, rubber, construction materials, cosmetics, soap, flooring, ink, plastic, polishers and whiteners, leather finishes, textiles, wallboard, white glue, and others.

Important ore sources for titanium and its derivative pigments are ilmenite, or iron titanate, and rutile. Ilmenite is found in the sand deposits in New Jersey, Virginia and Florida, and in India, Australia, South Africa, Malaya, and Senegal. Rutile is a naturally occurring titanium dioxide and is found in igneous, metamorphic and sedimentary rock. Major ore sources are along the east coast of Florida and in Virginia, although the largest deposits are in Australia where rutile is found in beach sands in combination with ilmenite.

The Titanium Products Division of National Lead, later to become NL Industries, remained a major producer of TiO2 pigments throughout the 20th century, holding the number-one position in the industry until the late 1970s. At that time, an environmental action filed by the U.S. government aimed at cleaning up the St. Louis and New Jersey plants forced NL to divest parts of its TiO2 business and shut down its U.S. production capacity. DuPont, meanwhile, continued to expand its TiO2 production plants and became the biggest supplier worldwide.

Other major domestic producers included American Cyanamid Co. and, later, SCM Corp. (now Millennium Chemicals). The Sherwin-Williams Co., and PPG Industries Inc. briefly entered the industry as well, in an effort to "back integrate" their operations into a key raw material for coatings. Energy powerhouse Kerr-McGee Corp. in mid-century developed its own TiO2 business from the ground up. Key overseas producers included British Titanium (later Tioxide) and Kemira.

DuPont pioneered the chloride-process TiO2 technology, which gradually replaced the original sulfate process and produced brighter, whiter pigments and boosted opacity while sharply reducing waste generation. Today, only a portion of Kerr-McGee's TiO2 production complex in Savannah, GA, operates with the sulfate process, with the chloride method used for all other domestic production.

Currently, the global TiO2 industry is dominated by U.S.-based producers, led by DuPont with more than 1 million metric tons of annual capacity. The other big suppliers are Millennium, with 712,000 mt; Kerr-McGee, with about 660,000 mt; Tioxide (now owned by U.S.-based Huntsman Corp.), with 550,000 mt; and NL's Kronos, with 440,000 mt. Japan's Ishihara is a distant sixth in the global TiO2 pecking order, with less than 200,000 mt of capacity.

DuPont’s Kuan Yin production site in Taiwan.

DuPont: 70 Years of Supplying TiO2

DuPont has been making titanium-based white pigments for paper, coatings, plastics and specialty applications since 1931 and is currently the world's largest producer of titanium dioxide (TiO2).

DuPont traces its beginnings in the TiO2 marketplace to its 1920 acquisition of the Krebs Pigment & Chemical Company of Newport, DE, a purchase designed to strengthen DuPont's position in the pigments market. Founded in 1902, Krebs Pigments and Chemical produced lithopone, a widely used white-paint pigment also manufactured by DuPont.

But the Krebs company had another asset of special interest to DuPont - a license to use a competing, more expensive and more effective white pigment, titanium dioxide. The Krebs license covered the use of TiO2 only as an extender or additive to lithopone pigments, not the manufacture of TiO2 itself, but the Krebs acquisition offered DuPont an initial foothold in the TiO2 market.

In 1931 DuPont formed a joint venture, the Krebs Pigment and Color Corporation, with the Commercial Pigments Corporation in order to develop a TiO2 production process. In 1934 DuPont purchased the Commercial Pigments Corporation's 30-percent minority interest in Krebs Pigment and Color, making the latter a wholly owned DuPont subsidiary, the Krebs Pigment and Color Corporation. DuPont placed the new subsidiary in its Krebs Pigments Department, which it renamed the Pigments Department in 1942 when it dissolved Krebs Pigment and Color Corporation's assets and transferred them into the DuPont Company. DuPont's TiO2-based Ti-Pure® white pigment eventually became one of the company's most successful products.

When demand surged after World War II, DuPont engineers invented an alternate, more economical "chloride process" to manufacture TiO2. Introduced at DuPont's Edgemoor, DE, plant in 1948, the chloride method gradually replaced the sulfate process in all DuPont TiO2 plants as they expanded to meet increasing demand through the 1990s. Reflecting the global scope of its TiO2 business, DuPont opened a TiO2 plant in Taiwan in 1994 and a technical service center in Mechelen, Belgium, in 1995 to serve the European, Middle Eastern and Asian markets.

Today, DuPont operates TiO2 plants in EdgeMoor, DE; New Johnsonville, TN; DeLisle, MS; Kuan Yin, Taiwan; and Altamira, Mexico. The company produces about a quarter of the world's TiO2 pigments.

Editor's Note: This is the first of an ongoing series of historical sketches about important developments in the coatings industry during the 90 years that Paint & Coatings Industry (PCI) and its predecessor magazines have been published.

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